Organische Synthesen mit Übergangsmetallkomplexen, 6: Ketenimin‐Synthese via Ketenimin‐Komplexe, Isocyanid‐Carben‐Addition sowie Ketenimin‐Carben‐Umlagerung in Metallkomplexen
- 1 March 1978
- journal article
- anorganische chemie
- Published by Wiley in European Journal of Inorganic Chemistry
- Vol. 111 (3) , 1223-1227
- https://doi.org/10.1002/cber.19781110341
Abstract
Organic Syntheses by Means of Transition Metal Complexes, 6: Synthesis of Ketenimines via Ketenimine Complexes, Isocyanide Carbene Addition and Ketenimine Carbene Rearrangement in Metal ComplexesTransition metal carbene complexes of the Fischer type, e. g. pentacarbonyl(methoxymethyl‐carbene)chromium(0), add isocyanides to give ketenimine complexes (1). Ligand displacement by excess isocyanide affords ketenimines (3), which can be isolated in good yields. In contrast to free ketenimine, the nucleophilic attack on ketenimine coordinated to a metal occurs at the terminal carbon atom leading to carbene complexes. The structures of the ketenimine complexes of chromium (1) and tungsten (2), the product of isomerization (5)(2) of the chromium complex, and the products formed by addition of methanol or water (6 and 7, resp.)(2) are discussed, using 13C NMR data.Keywords
This publication has 9 references indexed in Scilit:
- Rhodium carbene complexes. The structure of chlorobis(triphenylphosphine)tris(ethoxycarbonyl isothiocyanato)rhodium and the synthesis and proposed mechanism of formation of this and related complexesJournal of the American Chemical Society, 1977
- δ‐Lactone durch Carbonylierung von VinyloxiranenAngewandte Chemie, 1977
- Übergangsmetall‐Carben‐Komplexe, LXV. Über die Reaktion von Chlorwasserstoff und Bromwasserstoff mit Aminocarben‐pentacarbonyl‐Komplexen des Chroms und WolframsEuropean Journal of Inorganic Chemistry, 1973
- Structure and mechanism of formation of a novel .pi.-bonded ketenimine complex, bis(tert-butyl isocyanide) (N-tert-butyldicyanoketenimine)nickel(0). Evidence for a metal-assisted carbene additionJournal of the American Chemical Society, 1973
- Kristall‐ und Molekülstruktur von Pentacarbonyl‐[cyclohexylamino‐(1‐methoxy‐vinyl)‐carben]‐chrom(0)European Journal of Inorganic Chemistry, 1970
- Reaktionen von Triphenylphosphin sowie dessen Hydrobromid und Dibromid, IV1) Reaktionen zwischen Triphenylphosphin‐dibromid und substituierten SäureamidenEuropean Journal of Organic Chemistry, 1968
- Übergangsmetall‐Carben‐Komplexe, IV. Addition von Isonitrilen an Methylmethoxycarben‐pentacarbonyl‐chrom(0)European Journal of Inorganic Chemistry, 1968
- The Synthesis and Reactions of an α-Lactam, 1-t-Butyl-3,3-dimethylazirididoneJournal of the American Chemical Society, 1964
- Nitrogen Analogs of Ketenes. II. Dehydrochlorination of Imino Chlorides1,2Journal of the American Chemical Society, 1954